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Physically possible? Sure. Can you expect it to work? That's where it get complicated.

It comes down to drivers. Apple doesn't put in drivers for cards it doesn't use in its systems, so you would face the problem of the new card not working in OS X. However, since Windows does have drivers for practically every graphics card, you could stick the card in and use it in Windows via Boot Camp.

Kash is quite correct about apple only providing drivers for a very few graphics cards, but i believe there is also a slight issue with having a card which is compatable with the MAC systems EFI BIOS... im not 100% sure on this point, as iv never tried sticking any card except the Mac approved ones into my machine. But iv been led to believe that these cards are different in some way to that of the standard off the shelf models.

For example the 8800GT which i have, is a Mac dedicated product, u cant stick it into a standard windows machine... and following this logic is why i dont think just any old PCI-E graphics card will work in the Mac Pro (even in Boot Camp Windows)...